Manganese tricarbonyl



United States Patent Ofitice 3,350,430 Patented Oct. 31, 1967 This application is a division of application Ser. No. 49,135, filed Aug. 12, 1960, now abandoned.

This invention relates to compounds and a process involving the use of a (halosulfonyl) cyclopentadienyl manganese tricarbonyl compound.

An object of our invention is to provide new organometallic compounds and processes for their preparation. A further object is to provide cyclopentadienyl manganese tricarbonyl derivatives and processes for their preparation. Additional objects will become apparent from a reading of the specification and claims which follow.

The objects of our invention are accomplished by providing novel compounds such as [(p-tolylsulfamoyl) cyclopentadienyl}manganese tricarbonyl, prepared by reacting (halosulfonyl) cyclopentadienyl managanese tricarbonyl with a primary or secondary amine. The reaction conditions employed are not critical, and the temperature and pressure used are dependent on the nature of the amine reactant. Thus, if the amine reactant is a gas as in the case of dimethylamine, the reaction is performed under pressure and at a relatively low temperature. On the other hand, with an amine which is a high boiling liquid, the reaction is performed at higher temperatures, and pressure is not necessary. Preferably, moisture is excluded from the reaction mixture since it tends to decrease the yield by reacting with the sulfonyl halide reactant. As an illustration of this form of our invention, there is presented the following example.

The preparation of (halosulfonyl)cyclopentadienyl manganese tricarbonyls, the starting materials in this invention, as well as the preparation of other related cyclopentadienyl manganese tricarbonyl compounds, is fully described in our copending applications Ser. No. 283,139, and Ser. No. 283,140, filed May 13, 1963, now respectively US Patents Nos. 3,205,245, and 3,205,246, issued Sept. 7, 1965.

Among the important uses of our compounds is their as fuel and oil additives. For example, they are useul antiknocks when added to gasoline. They may be used is primary antiknocks in which they are the major anti knock component in the fuel or as supplenmental antiknocks. When used as supplemental antiknocks, they are present as the minor antiknock component in the fuel in addition to a primary antiknocl: such as a tetraalkyllead compound. Typical alkyllead compounds are tetraethyllead, tetrabutyllead, tetramethyllea-d and various mixed lead alkyls such as dimethyldiethyllead, diethyldibutyllead and the like. When used as either a supplemental or primary antiknock, our compounds may be present in the gasoline in combination with typical scavengers such as ethylene dichloride, ethylene dibromide, tricresylphosphate, trimethylphosphate and the like.

The compounds of our invention have further utility as additives to residual and distillate fuels generally, e.g., jet fuels, home heater fuels and diesel fuels, to reduce smoke ployed as additives to lubricating act to improve the lubricity of Our compounds are further useful in many metal plating applications. In order to effect metal plating using the compounds, they are decomposed in an evacuated space as to prevent oxidation of the plating metal or the object to be plated during the plating operations.

The gaseous plating technique described above finds wide application in forming coatings which are not only ecorative but also protect the underlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. A glass cloth band weighing one gram is dried for one hour in an oven at C. It is then placed in a tube which is devoid of air and there is added to the tube 0.5 gram of [(methylsulfonyl)cyclopentadienyl] manganese tricarbonyl. The tube is heated at 400 C. for one hour after which time it is cooled and opened. The clOth has a uniform metallic grey appearance and exhibits a gain in Weight of about 0.02 grams.

our compounds is their use as chemical intermediates in the preparation of metal-containing polymeric materials or in the preparation of new organic materials.

Having fully defined the novel compounds of our inventheir mode of preparation and their many utilities, We desire to be limited only appended claim.

We claim:

p Tolylsulfamoyl)cyclopentadienyl]manganese tricarbonyl.

References Cited UNITED STATES PATENTS Shriner et al..' Identification of Organic Compounds, John Wiley and Sons, Inc., New York, N.Y., 3rd edition (1948), p. 91.

TOBIAS E. LEVON, Primary Examiner. A. P. DEMERS, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,350,430 October 31, 1967 John Kozikowski et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, after line 38, insert the following example:

EXAMPLE I [Cyclopentadienyl sulfonyl chloride) manganese tricarbonyl (3 gm) and p-toluidine (3 gm) were mixed together and heated on a steam bath until a melt was formed. Ethanol (50 ml) was then added, the mixture heated to reflux for 15 minutes, cooled, diluted with potassium hydroxide aqueous solution and filtered. The filtrate was acidified with hydrochloric acid and the precipitate formed collected by filtration. Yield 2 g of yellow powder, m.p. l97-l99 which was [(ptolylsulfamoyl) cyclopentadienyl] manganese tricarbonyl. One crystallization from ethanol afforded yellow crystals, m.p. 199-201.

Anal. Calcd. for C15H MnNO S: C, 48.2; H, 3.27; Mn, 14 7; S, 8 .6, Found: C, 48 5 H, 3 .39; Mn, 14. 5 S, 9 2

Signed and sealed this 3rd day of December 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

